Preparation of synthetic resins



' Patented Dec. 14, 1943 2,336, 3 5 FICE PREPARATION OF SYNTHETIC RESIN S William J. Sparks, Elizabeth, and Donald 0. Field,

Linden, N. J., assignors to Standard Oil Development Company, a. corporation of Delaware No Drawing. Original application November 19,

1938, Serial No. 241,332. Divided and this application December 12, 1940, Serial No. 369,754

10 Claims.

This invention relates to novel synthetic resinous polymerization and condensation products containing combined halogen, and to methods for preparing them. It relates more particularly to the preparation of high molecular weight viscous to plastic, soluble products ,containing high concentrations of combined halogen and t the preparation of such products by subjecting suitable olefin halides or a mixture of such olefin halides and hydrocarbon aliphatic olefins to the action of active polymerization and condensation catalysts at low temperatures.

This application is a division of our co-pendin which X represents a halogen and R a hydrogen atom or an alkyl or aryl group. Examples of such compounds are allyl chloride, 2-methyl, 3-chlor propene or methallyl chloride, and other alkyl and aryl halo propenes such as 2-ethyl 3- chlor propene, 2-propyl 3-chlor propene, 2-ethyl S-brom propene, Z-phenyl 3-chlor propene and 2- naphthyl 3-chlor propene. The preferred alkyl halo propenes are the chlorides having from one to six carbon atoms in the alkyl group while the' preferred aryl halo propenes are chlorides containing a phenyl or naphthyl group which may itself be substituted. The aryl groups of such compounds may contain substituent groups attached to the aromatic nucleus such as alkyl, sulfate, amino or hydroxy groups.

It has been found that these olefin halides may be polymerized by the action of metal halide catalysts of the type used in the Friedel-Crafts syn thesis. The reaction is conducted at low temperatures below 0 C. to -10 C. and preferably at much lower temperature such as -40 or 50 to -80 C. The catalyst is preferably dissolved in a suitable organic liquid which is substantially inert under the conditions of the reaction; for example, aluminum chloride dissolved in ethyl chloride has been found particularly efiective in the processes of this invention.

It has also been found that valuable chlorinecontaining co-polymers of high molecular weight, which are also viscous to plastic, soluble products, can be formed by conducting the above-described reaction in the presence of low molecular weight olefins, preferably iso-olefins such as isobutylene,

Instead of isobutylene, other iso-olefins capable of polymerizing in a manner similar to the isobutylene may be used, such as Z-methyl butene-l, etc. Generally it is desirable to use such isoolefins having not more than about seven carbon atoms. Although it is preferred to use such isoolefins on account of their particular adaptability for polymerizing to extremely high molecular weight polymers, it is possible to useother readily polymerizable low molecular weight olefins, such as propylene or alpha or beta. butylene or substituted olefins such as vinyl ethyl ether.

The following examples are presented to illustrate suitable methods for preparing the improved resinous products of this invention.

EXAMPLE I Ten volumes of methallyl chloride were diluted with twenty volumes of ethyl chloride (CzI-IaCl) and the mixture was cooled with powdered carbon dioxide snow to 78 C. Four volumes of a concentrated solution of aluminum chloride in ethyl chloride, prepared at the boilingfpoint of ethyl chloride, was cooled to 78 C. an then added rapidly to the first mixture with stirring. A precipitate formed immediately which redissolved on standing for two hours. 'The reaction mixture was then diluted with alcohol to remove the catalyst and was permitted to warm up to room temperature thereby removing the ethyl chloride by evaporation. The residue was then dissolved in benzol and precipitated by the addition of ethyl alcohol. This procedure was repeated several times, yielding a product which was a pliable, rather hard resin which'softens considerably upon heating to about 200 F. The resin is of dark brown color and is soluble in liquid hydrocarbons, such as benzene, gasoline and in other solvents, such as carbon tetracnl orid and chloroform. It is insoluble in ethyl alcohol, water and acetone.

EXAMPLE lI Twelve parts by weight of isobutylene and nine parts of methallyl chloride were cooled with powdered carbon dioxide snow and diluted with an equal volume of propane. Five parts of a concentrated solution of aluminum chloride in ethyl chloride, prepared at the boiling point of ethyl chloride was cooled to 78 C. and then added slowly with stirring to the first mixture. A vigorous reaction ensued. After threeiminutes the reaction mixture was diluted with alcohol to remove the catalyst and was permitted to warm up to room temperature, thereby removing the ethyl chloride by evaporation. The residue was then dissolved in benzol and precipitated by the addition of ethyl alcohol. This procedure was repeated several times, the product finally precipitating from acetone being dried by heating in an oven at 100 C. This product was a water-white pliable, plastic solid having rubber-like properties. It gave a positive Beilstein test for chlorine. It is soluble in solvents such as benzene, gasoline, and carbon tetrachloride. It is insoluble in ethyl alcohol, water, and acetone.

The products prepared according to this invention have extremely high molecular weights, generally above about 1000 and usually of much higher molecular weight the order or 5000 to 50,000. It is believed that these products are characterized by the long carbon chain structure characteristic of the extremely high molecular weight polymers of isobutylene. For example, the products obtained by polymerization of methallyl chloride apparently have the following structure:

CHQCI CHQCI CHIC] JJ-OHrcm- Ha Ha HI while the co-polymers prepared from methallyl chloride and isobutylene apparently have the following structure:

on. orncl on, omen CH:-- CH: CHr- Hi m a. a

Both the methallyl chloride polymers and the co-polymers are characterized by the presence of chlorine in the primary positions only.

As the catalyst, instead of using aluminum chloride, other volatilizable Friedel-Crafts metal halides having a similar catalytic influence on polymerization and condensation reactions may be used. as, for instance, aluminum bromide, aluminum iodide, titanium tetrachloride, and the like, or complexes of these catalysts with organic compounds, such as ethyl chloride. Other com- Solubility of aluminum chloride in ethyl chloride '1 C tact ER)? emperon 55mph aturo time dissolved Ethyl chloride and excess aluminum 0. Min. Pn cent chloride 78 60 0.1 45 45 0.1 0 180 4. 4 +8 60 5. 4 +12 180 7. 4

After a substantial amount of aluminum chloride has been dissolved in desired amount up to the saturation point, the solution, it not already of .the proper concentration, may be ad- .lusted by dilution with further solvent and then cooled down to the desired temperature for the catalytic co-polymerization. If desired, the AlCla-CzI-IsCl, either separated as such or else dissolved in ethyl chloride, may be dissolved in or diluted with other solvents or diluents, such as methyl chloride, chloroform, etc.

In carrying out both the polymerization and the copolymerization reactions described above, one suitable procedure is to mix the materials to be polymerized in the desired proportions, either alone or with a suitable solvent, diluent, or refrigerant, such as liquefied ethylene, and then add the catalyst, such as a 5% solution of aluminum chloride in ethylchloride, either alone or dissolved in a suitable diluent such asliquefled ethylene. The use of liquefied ethylene for the several purposes mentioned has an additional advantage that it serves simultaneously as refrigerant to maintain the desired low temperature by absorption of the heat of polymerization by boiling oil some of the liquefied ethylene. If desired, the cooling may be effected by either internal or external cooling 00115 through which a suitable refrigerating liquid is passed or by having the reacting liquids fed into a pipe, coil, or other condenser immersed in a suitable refrigerated bath. However, instead of using such a vaporizable diluent or solvent, dry ice (solidified carbon dioxide) may be used as refrigerant merely by adding pieces of it to the reaction vessel. Owing to the desirability of maintaining a low temperature, it is preferred to have the catalyst, as well as the reactants, precooled to a temperature at least as low as the desired operating temperature. If dry ice is used as refrigerant, the operating temperature is about 78 C., whereas if liquefied ethylene is used as refrigerant, an operating temperature of about 95 C. is maintained (ethylene alone boils at 103 0.). It is possible to use even lower temperatures by using liquefied methane or mixtures thereof with other hydrocarbons.

If desired, the reaction may be carried out under pressure, either just sufiiciently above atmospheric to keep the reactant and solvent in the liquid phase or considerably higher pressures may be used, such as up to 10, 20, or 50 atmos-' pheres or more.

In the preparation of c'o-polymers, the proportions of the materials to be co-polymerized may vary over wide limits without departing from the to co-polymerization, the amount of chlorine in the finished product bearing a direct ratio to the proportion of methallyl chloride to isobutylene in the reacted mixture.

The products of this invention are soluble in hydrocarbon oils, generally, and the blends thereof with hydrocarbon oils have many advantages. The polymers are extremely effective, for example, in raising the viscosity and viscosity index of hydrocarbon oils when added thereto in small proportions of the order of a few per cent. They may be used, within the limits of their solubility as thickening agents for gasoline and other motor iuels, burning oils, and lubricants. They also serve as plasticizing agents for solid hydrocarbon compositions, such as waxes, asphalts, and the like. In lubricating oils they have the especial advantage of decreasing the change in viscosity oi the oil with rise in temperature. This is illustrated in the following example:

EXAMPLE HI Two per cent by weight of the co-polymer of methallyl chloride and isobutylene, prepared as described in Example 11, was added to an S. A. E. 20-W petroleum lubricating oil. The viscosity characteristics of the original oil and the resulting blend are given in the following table:

Saybolt viscosity,

seconds Viscosity index E. 20-W 276 E. 20-W+2% co-polymer 518 S. A. S. A. 62.

The products of this invention may also be added in small amounts, of about 0.05 to by weight, to lubricating greases and are very effective in imparting stringy and adhesive characteristics to such greases, including lime, soda, aluminum, and mixed bases.

An illustration of the use of these products in greases is given in the following example:

Exmrra IV Dissolve 10% by weight of a co-polymer of isobutylene and methallyl chloride, prepared as in Example II, in a mineral lubricating oil of high viscosity index by stirring and heating to 200 F. After complete solution, add 1% of this solution to a lubricating soap grease, such as a mixed base The addition of the products of this invention 1 to lubricating oils and greases, as described above, also increases the ability of such lubricants to carry heavy loads and renders them efiectlve lubricants under the conditions of extreme pressure encountered in the lubrication of hypoid gears and the like. Sulfur and organic sulfur compounds may also be added to such lubricants or the polymerization and oo-polymerization products described herein may themselves be sulfurized, as by. heating with sulfur or sulfur chloride.

The halogen content of the polymerization and co-polymerization products of this invention can be increased by halogenation of such products. For example, these products may be chlorinated by a direct reaction with chlorine either in gaseous or dissolved state. The chlorination is preferably carried out with the products dissolved in an inert solvent, such as carbon tetrachloride.

Chlorine may be bubbled through this solution under atmospheric pressure or at higher or lower pressures, or the solution may be passed in a thin film or spray through a chamber filled with chlorine gas. The chlorination may be conducted in the absence of light or other catalyzing influence, or it may be conducted in the presence of sunlight or even stronger sources of ultra-violet light, such as a mercury vapor lamp, or in the presence of light of a carbon'arc lamp, or of other light of any-desired wave length, or in the presence of other catalysts, such as iodine, antimony halides, and ferric chloride, or of peroxides, such as benzoyl peroxide, which directs the halogen atoms preferentially to the alpha (end) carbon atoms in the molecule. Mixtures of such catalytic influences may also be used.

Suitable temperatures for the chlorination include from about 50 to 100 C. and range preferably from between about 25 C. and the boiling point of carbon tetrachloride, about 78 C. For temperatures below the melting point of carbon tetrachloride, a mixture such as one part of carbon tetrachloride and three parts of chloroform may be used. By these means products having chlorine contents as high at 50 to 75% are prepared, depending upon the intensity of the chlorination conditions and the time of exposure of the materials to be chlorinated.

If desired the products may be freed from any corrosive constituents, such as free chlorine or decomposition products that may be present, by

incorporating therewith a basic material which may also serve as a stabilizer, such, for example, as an aromatic amine, monoethyl aniline, methyl naphthylamine, or a quaternary ammonium base, such as tetramethyl ammonium hydroxide. The products may also be washed with an alkaline solution, such as a 10% solution of sodium hydroxide or sodium carbonate.

The polymerization and co-polymerization products of this invention, whether subjected to additional halogenation or not, are stable toward sunlight and artificial ultra-violet light, air, hot and cold water, and chemical agents, such as solutions of acids, bases, and salts.

The polymerization and co-polymerization products of this invention have the characteristics, depending on their molecular weight, of viscous liquids to plastic elastic solids. Increasing the halogen content of these products, as by chlorination, increases their toughness, chlorinated products of high molecular weight and having chlorine contents as high as 60 to 75% being obtained in the form of brittle solids or powders.

The co-polymers of methallyl chloride and isobutylene are soluble in the following solventsi Diphenyl oxide Carbon tetrachloride Vistone" (isopropyl ester Chloroform of fatty acids produced Mono amyl naphthalene by oxidation) Dimethyl naphthalene Benzene Dowtherm A" (diphenyl Toluene oxide and di henyl) Xylene Sec-hexyl chlor de y Nitrobenzene Tetrachlorethane Ethyl benzene Turpentine Scc-lrutyl benzene Tetralin Pyridine Trimethyl aniline Mono chlorbenzene Methanol Sec-butyl ethyl ether Ethanol N-butyl ether Isopropyl alcohol Di-isopropyl ether Butanol Tert-butyl ethyl ether Tert-amyl alcohol Ethyl lactate Sec-hexyl alcohol Isopropyl lactate Heptyl alcohol Butyl lactate Benz 1 alcohol Ethyl oxalate Ethy ene glycol Triethyl citrate Triethyl aniline Ethyl'aceto acetate The polymers of methallyl chloride have in general the same solubility characteristics as the co-polymers, but are less soluble in simpleoxyorganic solvents of low molecular weight, such as acetone, ethyl ether, ethyl acetate, etc.

The polymers and co-polymers of this.lnvention may be compounded with the following resinous, asphaltic, and waxy materials:

Drying oil-modified alkyd, Rosin rosin ,Linied, rosin Hydrocarbon resins from iolystyrol petroleum oils l'ure phenollcs Run Congo copzil l'oiy indene (umar Polyvinyl acetate llenzyl cellulose Methyl methncrylate l'arex: resin Asphalt East India gum iqtl Singapore damrnar Batu East India ('fyclopenmdiene resin Modified phenolic resin Alkyd maicic resin Ester gum Chinese insect wax Utah gilsonite Japan wax Coal tar ()zokerlte wax Araclors (chlorinated di- Candleilla wax (arnauba wax Chlorinated rubber Spermaceti wax Stcaric wax They are partially compatible with ethyl cellulose and are incompatible with:

Cellulose acetate Gum elcini Shellac Manila gum Polyvinyl chloride The polymers and co-polymers of this invention may be compounded with the following ma.- terials commonly used as plasticizers:

Dimethyl phthalate Raw perilla oil Dietliyl phthalate Raw rape seed oil Dibutyl phthalate Methyl phthalyl ethyl gly- Trlbutyl phosphate collate Butylll phthalyl ethyl gly- Triphenyl phosphate Tricresyl phosphate c e Methyl cyclohexyl adipate Benzyl benzoate Dibutyl tartrate Triacetin Butyl stearate Amyl stearate Butyl acetyl ricinoleate Camphor Amyl oleate Blown linseed oil Raw castor oil Raw linseed oil Boiled linseed oil Boiled tung oil Raw tung oil Raw soy bean oil Blown soy bean oil Raw cottonseed oil Raw sardine oil They are incompatible with linseed oil fatty acids and with tung oil fatty acids.

As indicated above, the polymerization and copolymerization products of this invention are high molecular weight hydrocarbons containing substantial proportions of combined halogen and are either viscous liquids or solids or substances of, more or less, intermediate characteristics in the nature of plastic solids, depending on the nature of the original material treated, the duration and type of treatment, and the extent 0! any further halogenation. These products may be used for a wide variety of purposes. For example, they may be used as fire-resistant agents, for impregnating various types of porous or iibrous materials, such as cloth, paper, and building materials. They may also be mixed with inert organic materials and added to solutions of artificial silk for the purpose of delustering the silk product. They may also be incorporated with wax and used for impregnating wood for preservation purposes.

They are soluble in many volatile solvents which are used in the preparation of coating compositions of various kinds, and may be used therewith, alone, or in conjunction with other materials, such as drying oils, pigments, and the like, in the preparation of paints, varnishes, lecquers, enamels, etc.

The polymers prepared according to this invention may be employed as plastics, adhesives,

resins, impregnating or coating materials, table coatings, insulating compounds, lubricating oil thlckeners, etc., or they may be added in proportlons of 5, 10, 50 or even 95% to rubbers such as natural rubber, polychlorprene, polyolefine sulfide type rubber, ethylene dichloride-benzol type rubber, polysulfones, polystyrol, polyvinyl compounds, polyacrylates, polydiolefines, chlorinated or fluorinated polymers, resins, cellulose compounds, rubber hydrochlorides or haloformed rubbers of the Pliolite type. They may be vulcanized with the above compounds to give rubbery or ebonite-like products.

The halogen atoms attached to the polymer or co-polymer may also be subjected to metathetical reactions to give modified products having hydroxyl, nitrile,mercapty1, or ester groups in place of the chlorine atoms.

This invention is not to be limited to any specific examples or theoretical explanation presented above, all such being intended solely for purpose of illustration, but is to be limited only to the following claims in which it is desired to claim all novelty insofar as the prior art permits.

We claim:

1. Process for preparing improved viscous liquid to solid resinous products having a molecular weight of at least about 1,000, comprising subjecting a. mixture of an iso-olefin containing less than about 8 carbon atoms in the molecule and an olefin halide represented by the formula in which X represents a halogen and R represents a member of the group consisting of hydrogen,-

CHIC] in which R represents an alkyl group, to the action of a solution of aluminum chloride in a halogenated hydrocarbon solvent, at a temperature below about --40 C.

5. Process according to claim4 in which said halogenated hydrocarbon solvent is ethyl chloride.

6. Process according to claim 4 in which said halogenated hydrocarbon solvent is methyl chloride.

7. Resinous products containing combined halogen and having the properties of viscous liquids to solids having a molecular weight of at least about 1,000, produced by co-polymerization of a mixture of an iso-olefln containing less than about 8 carbon atoms in the molecule and an olefin halide represented by the formula CHr-X in which X represents a halogen and R represents a member of the group consisting of hydrogen atoms, alkyl groups, and aryl groups, in the presence of a metal halide catalyst of the Friedel- Crafts type at a temperature below about 0 C.

8. Resinous products containing combined chlorine and having the properties of a viscous liquids to solids having a molecular weight of at least about 1,000, produced by co-polymerization of an iso-olefin having less than about 8 carbon atoms and an olefin chloride represented by the formula CHIC in which R is an alkyl group, in the presence of a solution of aluminum chloride in a halogenated hydrocarbon solvent at a temperature below about -40 C.

9. Resinous products containing combined halogen and having the properties of viscous liquids to rubber-like plastic solids, produced by copolymerization of a 2-alkyl, 3-chlorpropene-l, and an iso-olefin of less than about 8 carbon atoms in the molecule, in the presence of a metal halide catalyst of the Friedel-Crafts type at a temperature below 0 C.

10. Resinous products containing combined halogen and having the properties of viscous liquids to rubber-like plastic solids, produced by copolymerizatlon of a 2-alkyl; 3-chlorpropene-1, and isobutylene in the presence of a metal halide catalyst of the Friedel-Crafts type at a tempera- WILLIAM J. SPARKS. DONALD C. FIELD.

l6 ture below about 0 C. 

